DE102020006977A1 - Aqueous-alcoholic polyester compositions, detergents and cleaning agents containing these and their use - Google Patents

Abstract

Aqueous-alcoholic compositions of selected anionic polyesters and selected nonionic polyesters are described. These compositions are characterized by good storage stability and low viscosity and can be used in detergents and cleaning agents to improve the dirt-removing power.

Description

Aqueous-alcoholic polyester compositions, detergents and cleaning agents containing these and their use

The invention relates to aqueous-alcoholic compositions of selected polyesters which are suitable as additives for detergents and cleaning agents and which are distinguished by very good dirt-removing power.

The use of polyesters in detergents to improve the removal of dirt from textiles, to reduce resoiling, to protect the fibers under mechanical stress and to finish the fabric and to make it more comfortable to wear is known. A large number of polyester types and their use in detergents and cleaning agents are described in the patent literature. These polyesters are generally known under the term SRP or “soil-release polyester”.

Examples of such polyesters can be found in US 4,702,857A , US 4,427,557A , US 4,721,580A , US 4,968,451A , WO 96/18715 A2 , US 5,415,807A , U.S. 5,691,298 , DE199 06 367 A1 , WO 98/05747 A1 , US 5,599,782 A , WO 94/22937 A1 , EP 1 966 273 B1 and EP 2 504 380 A1 .

Polyesters with improved soil release properties can contain anionic groups and/or nonionic groups. These can occur as end groups in the polyester molecule or they are residues that occur in the groups that build up the polymer backbone. An example of anionic radicals are sulfonic acid groups; these can occur, for example, in 5-sulfoisophthalic acid residues or as end groups derived from isethionic acid. An example of nonionic residues are polyethylene glycol residues; these can occur, for example, in the polymer backbone of the polyester or as end groups.

Polyesters with improved protective release properties, in particular anionic polyesters, often cannot be stored dissolved in water. These polyesters are constructed in such a way that they can be drawn onto a polymer fiber from an aqueous medium, for example a washing liquor. For this, the structure of these polyesters must be hydrophilic enough to be able to be transported in water; on the other hand, however, this polyester must also be hydrophobic enough to be able to be absorbed onto the fibers (cf. Powdered Detergents, E. Gosselink; Surface Science Series; Volume 71, p. 205 et seq. (1998)).

Because of these properties, the polyester molecule is aggregated in water even though it appears dissolved. A consequence of this "semi-solubility" is a crystallization of the polymer chains "in solution". Larger aggregates are formed, which scatter the light, making the dispersion opaque and appearing white. Unfortunately, as the crystallization progresses, the viscosity of the medium also increases, since larger and larger aggregates are formed. This can lead to a firm consistency.

For the processing and use of polyesters with dirt-removing properties, it is important that they can be stored as aqueous compositions and that the increase in viscosity is kept within limits.

The fact that concentrates can be produced from SRP with a selected structure in organic/aqueous media is, for example, in WO 2011/063945 A1 described. This document describes aqueous concentrates of special anionic polyesters that can be stored for a certain period of time. The aim of the invention described in this document was to develop polyester structures based on sulfo-containing monomers which, on the one hand, show very good graying-inhibiting performance when used in liquid detergents and, on the other hand, show only minimal tendency to crystallize in aqueous solution and are storage-stable as a solution. These polymer solutions, referred to as concentrates, should be suitable for use in liquid detergent formulations and should be as clear and low-viscous as possible. In the WO 2011/063945 A1 The solution described is to use selected sulfo-containing polyesters with a specific ratio of propylene glycol to ethylene glycol units.

A further possible measure for stabilizing aqueous SRP compositions is the addition of selected organic solvents. So reveals the EP 3167032 B1 Compositions containing selected nonionic polyesters, selected water-miscible alcohols and water. These compositions are distinguished by increased storage stability. Also in the above mentioned WO 2011/063945 A1 are storage-stable polyester concentrates disclosed by dissolving the appropriate amount of selected anionic polyesters in water or in a combination of water with water-miscible solvents such as propylene glycol or ethylene glycol. However, there is no indication in this document that further polymers can be used to stabilize the compositions in addition to anionic polyesters.

In the case of anionic SRP, however, it has been shown that the addition of water-miscible solvents does not always promise success. For example, an aqueous composition of a polyester was investigated which has ethylene glycol terephthalate and propylene glycol terephthalate units and end groups derived from isethionic acid and from polyethylene glycol monomethyl ether. Water-miscible organic alcohols were added to this aqueous composition. It was shown that after a few hours the viscosity at 25°C increased from an initial few 100 mPa*s to values outside the measuring range of the Brookfield method. In this form, this product cannot be handled or processed properly.

Proceeding from this state of the art, the object of the present invention was to provide SRP compositions which are stable over a long period and whose viscosity does not change or does not change appreciably even after prolonged storage.

Another object of the present invention was to provide stable, low viscosity SRP compositions.

Surprisingly, it was found that the viscosity of aqueous-alcoholic compositions of anionic SRP can be reduced by adding nonionic SRP and that the compositions stabilized in this way can be stored for months without their viscosity increasing excessively. Compositions according to the invention do not thicken and remain stable for several months even when stored at elevated temperatures.

1. A) mindestens einen anionischen Polyester erhältlich durch Polymerisation der Komponenten
   1. a) ein oder mehrere sulfogruppenfreie aromatische Dicarbonsäuren und/oder deren Salze und/ oder deren Anhydride und/oder deren Ester,
   2. b) gegebenenfalls ein oder mehrere sulfogruppenhaltige Dicarbonsäuren, deren Salze und/oder deren Anhydride und/oder deren Ester,
   3. c) ein oder mehrere aliphatische Diole der Formel (1) H-(OC_mH_2m)_sOH (1), wobei m eine Zahl von 2 bis 10 ist und m innerhalb eines Moleküls im Rahmen der gegebenen Definition unterschiedliche Bedeutungen annehmen kann, s eine Zahl von 1 bis 200 ist, wobei s mindestens 1 bedeutet und zusätzlich einen Wert zwischen 2 und 200 annehmen kann,
   4. d) gegebenenfalls ein oder mehrere Verbindungen der Formel (2) R¹O(C_oH_2oO)_pH (2) wobei R¹ für eine lineare oder verzweigte Alkylgruppe mit 1 bis 22 C-Atomen steht, o eine Zahl von 2 bis 10 ist und o innerhalb eines Moleküls im Rahmen der gegebenen Definition unterschiedliche Bedeutungen annehmen kann, p eine Zahl von 1 bis 200 ist,
   5. e) gegebenenfalls ein oder mehrere Verbindungen der Formel (3) und/oder der Formel (4) R²(C_qH_2qO)_rH (3), (Me^a+)_b ^-O₃S-C₆H₄-COOR¹⁰ (4), wobei q eine Zahl von 2 bis 10 ist, r für eine Zahl 1 bis 10 und R² für einen Rest (Me^a+)_b ^-OOC- oder (Me^a+)_b O₃S- steht, R¹⁰ Wasserstoff oder C_1-C₆-Alkyl bedeutet, Me für Wasserstoff oder ein a-wertiges Kation steht, a eine Zahl von 1 bis 3 bedeutet, b eine Zahl mit dem Wert 1/a ist, und
   6. f) optional ein oder mehrere vernetzend wirkende polyfunktionelle Verbindungen, mit der Maßgabe, dass mindestens eine der Komponenten b) oder e) vorhanden ist,
2. B) mindestens einen nichtionischen Polyester erhältlich durch Polymerisation der oben definierten Komponenten a), c), d) und gegebenenfalls f),
3. C) ein oder mehrere aliphatische oder cycloaliphatische Alkohole mit 1-20 Kohlenstoffatomen, und
4. D) Wasser.

The present invention relates to compositions containing

1. A) at least one anionic polyester obtainable by polymerizing the components
   1. a) one or more sulfo-free aromatic dicarboxylic acids and/or their salts and/or their anhydrides and/or their esters,
   2. b) optionally one or more dicarboxylic acids containing sulfo groups, their salts and/or their anhydrides and/or their esters,
   3. c) one or more aliphatic diols of formula (1) H-(OC _m H _2m ) _s OH (1), where m is a number from 2 to 10 and m can have different meanings within a molecule within the scope of the given definition, s is a number from 1 to 200, where s is at least 1 and can also have a value between 2 and 200,
   4. d) optionally one or more compounds of formula (2) R ¹ O(C _o H _2o O) _p H (2) where R ¹ is a linear or branched alkyl group having 1 to 22 carbon atoms, o is a number from 2 to 10 and o can have different meanings within a molecule within the scope of the given definition, p is a number from 1 to 200,
   5. e) optionally one or more compounds of the formula (3) and/or the formula (4) R ² (C _q H _2q O) _r H (3), (Me ^a+ ) _b ^-O3 _SC6 ^H4 _-COOR10 ( ₄ ), where q is a number from 2 to 10, r is a number from 1 to 10 and R ² is a radical (Me ^a+ ) _b ^- OOC- or (Me ^a+ ) _b O ₃ S-, R ¹⁰ is hydrogen or C _1- C ₆ alkyl, Me is hydrogen or an a-valent cation, a is a number from 1 to 3, b is a number with the value 1/a, and
   6. f) optionally one or more crosslinking polyfunctional compounds, with the proviso that at least one of components b) or e) is present,
2. B) at least one nonionic polyester obtainable by polymerization of the components a), c), d) and optionally f) defined above
3. C) one or more aliphatic or cycloaliphatic alcohols having 1-20 carbon atoms, and
4. D) water.

The proportion by weight of the total amount of polyesters A and B in the compositions according to the invention is usually 1 to 50%, preferably 5 to 40%, in particular 10 to 30% and very particularly preferably 15 to 25%, based on the total amount of the composition.

The proportion by weight of the total amount of (cyclo)aliphatic alcohols having 1-10 carbon atoms in the composition according to the invention is usually 20 to 95%, preferably 40 to 80%, in particular 60 to 70% and very particularly preferably 50 to 65%, based on the total amount the composition.

The proportion by weight of water in the composition according to the invention is usually 1 to 50%, preferably 2 to 30%, in particular 5 to 20% and very particularly preferably 7 to 15%, based on the total amount of the composition.

In addition to the polyesters A and B, the composition according to the invention contains water-soluble or water-miscible (cyclo)aliphatic alcohols, water and optionally other additives such as water-miscible non-alcoholic organic solvents, e.g. acetone, surfactants, dyes, fragrances or buffer substances.

The proportion by weight of the total amount of optional further additives in the composition according to the invention is usually 0 to 20%, preferably 0 to 10%, and very particularly preferably 0 to 5%, based on the total amount of the composition.

The proportion by weight of polyester A, based on the total mass of polyesters A and B in the compositions according to the invention, is usually from 1 to 99%, preferably from 20 to 80% and particularly preferably from 35 to 60%.

The proportion by weight of polyester B, based on the total mass of polyesters A and B in the compositions according to the invention, is usually from 99 to 1%, preferably from 80 to 20% and particularly preferably from 65 to 40%.

Monomer component a) is a sulfo-free aromatic dicarboxylic acid and/or its salt and/or its anhydride and/or its ester. Preferred compounds of monomer component a) are terephthalic acid, in particular the C1-C4- _{dialkyl esters} of terephthalic acid, for example dimethyl terephthalate, and also isophthalic acid and C1-C4- _{dialkyl esters} of isophthalic acid or naphthalenedicarboxylic acid and C1-C4- _{dialkyl esters} of naphthalenedicarboxylic acid. The monomer component a) forms the backbone of the polyester used according to the invention.

The monomer component b) is a sulfo-containing dicarboxylic acid, its salts and/or its anhydrides and/or its esters. Preferred compounds of monomer component b) are 5-sulfoisophthalic acid, especially 5-sulfoisophthalic acid di(C ₁ -C ₄ )alkyl esters and alkali metal salts thereof, for example alkali metal salts of 5-sulfoisophthalic acid and dimethyl 5-sulfoisophthalate sodium salt or lithium salt. The monomer component b) forms the backbone of the polyester used according to the invention.

The monomer component c) is an aliphatic diol of the formula (1) defined above. These can be straight-chain or branched aliphatic diols. Diols of the monomer component c) are alkylene glycols which are optionally used together with polyoxyalkylene compounds. In the context of this description, polyoxyalkylene compounds are to be understood as meaning homo- or copolymers derived from alkylene oxides. If there are different alkylene oxide units in the molecule, for example units derived from ethylene oxide and from propylene oxide, the different units can be randomly distributed in the polymer or else in the form of blocks. An example of a block copolymer is an ethylene oxide/propylene oxide block copolymer. If different alkylene oxide units are present in the molecule, these are cases in which m can assume different meanings within the scope of the definition given. Only alkylene glycols (index s=1) are preferably used, very particularly preferably only ethylene glycol.

Index s is preferably a number from 1 to 50, in particular from 1 to 20, very particularly from 1 to 10 and most preferably 1.

Preferred compounds of monomer component c) are ethylene glycol, propylene glycol, especially 1,2-propylene glycol.

Polyoxyalkylene compounds used with preference are polyoxyethylene compounds having 2 to 20, in particular 2 to 10, ethyleneoxy repeating units or polyoxypropylene compounds having 2 to 20, in particular 2 to 10, propyleneoxy repeating units.

Further preferred monomer components c) are mixtures of ethylene glycol and ethylene oxide-propylene oxide block copolymers of the formula H-(OCH ₂ CH ₂ ) _q1 -]-[(OCH ₂ CH(CH ₃ )) _p1 ]-OH wherein
q1 is a number from 12 to 120 and
p1 is a number from 11 to 60, preferably from 15 to 50, and more preferably from 20 to 40. Polyester derived from these monomer components are, for example, from the EP 2670786 B1 famous.

If mixtures of alkylene glycols and polyoxyalkylene compounds are used, the molar mixing ratio of alkylene glycols to polyoxyalkylene compounds is usually from 20:1 to 1:1, preferably from 10:1 to 5:1. The monomer component c) forms the backbone of the polyester used according to the invention.

The monomer component d) is a compound of the formula (2) defined above. These can be straight-chain or branched aliphatic compounds. Preferred compounds of the monomer component d) are alkylene glycols with end caps on one end or polyoxyalkylene compounds with end caps on one end. In the context of this description, polyoxyalkylene compounds are to be understood as meaning homo- or copolymers derived from alkylene oxides. If there are different alkylene oxide units in the molecule, for example units derived from ethylene oxide and from propylene oxide, the different units can be randomly distributed in the polymer or else in the form of blocks. An example of a block copolymer is an ethylene oxide/propylene oxide block copolymer. If different alkylene oxide units are present in the molecule, these are cases in which o within a molecule can assume different meanings within the scope of the given definition. Ethylene glycol monomethyl ether, polyoxyethylene monomethyl ether with average molecular weights of 200 to 2000 g/mol or poly[ethylene oxide-copropylene oxide] monomethyl ether with average molecular weights of 100 to 20,000 g/mol, preferably 500 to 10,000 g/mol, are preferred. The monomer component d) forms end groups of the polyester used according to the invention.

Index o is preferably a number from 2 to 4 and in particular from 2 to 3.

Index p is preferably a number from 1 to 50, in particular from 1 to 20, very particularly from 1 to 10 and most preferably from 2 to 3.

Further preferably used monomer components d) are mixtures of ethylene glycol and ethylene oxide-propylene oxide block copolymers of the formula which are end-capped at one end R ¹ -(OCH ₂ CH ₂ ) _q 1 -]-[(OCH ₂ CH(CH ₃ )) _{p 1} ]-OH wherein
R ¹ has the meaning defined above, preferably C _1-6 -alkyl, in particular methyl,
q1 is a number from 12 to 120 and
p1 is a number from 11 to 60, preferably from 15 to 50, and more preferably from 20 to 40. Polyester derived from these monomer components are, for example, from the EP 2670786 B1 famous.

The monomer component e) is a compound of the formulas (3) and/or (4) defined above. The compounds of formula (3) can be straight-chain or branched aliphatic compounds. Preferred compounds of the formula (3) are those of the formula H-(OCH ₂ CH ₂ ) _r1 -SO ₃ X, where r1 is a number from 1 to 4, particularly preferably 1 and 2, and X is hydrogen, sodium or potassium, stands. The compounds of formula (4) are derivatives of sulfobenzoic acid. This can be the free sulfobenzoic acid, its salts or esters, in particular the free acid, its alkali metal or alkaline earth metal salts or its alkyl esters. The sulfo group can be in the 2-, 3- or 4-position of the phenyl ring, preferably in the 3-position. Preferred compounds of the formula (4) are those of the formula XO ₃ SC ₆ H ₄ -COOR ¹⁰ , where X is hydrogen, sodium or potassium and R ¹⁰ is as defined above.

Index q is preferably a number from 2 to 4 and in particular from 2 to 3.

Index r is preferably a number from 1 to 5, in particular from 1 to 4 and very particularly from 1 to 3.

The monomer component e) forms end groups of the polyester used according to the invention.

Me in the formulas (3) and (4) is preferably hydrogen or a mono- to trivalent cation, preferably hydrogen, an alkali metal cation, an alkaline earth metal cation or an ammonium cation.

The monomer component f) is a crosslinking polyfunctional compound. The monomer component f) forms the backbone of the polyester used according to the invention. Preferred compounds of monomer component f) are crosslinking polyfunctional compounds having at least 3, in particular 3 to 6, functional groups capable of the esterification reaction, for example acid, alcohol, ester, anhydride or epoxy groups. Different functionalities are also possible in one molecule. Preferred examples thereof are citric acid, malic acid, tartaric acid and gallic acid, particularly preferably 2,2-dihydroxymethylpropionic acid. Polymeric crosslinkers can also be used, for example polyacrylic acid, polymaleic acid or maleic acid-ethylene copolymers.

It is also possible to use trihydric or higher alcohols, such as pentaerythrol, glycerol, sorbitol and trimethylolpropane, as monomer component f).

Further preferred monomer components f) are tribasic or higher aliphatic and aromatic carboxylic acids, such as benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid), particularly preferably benzene-1,3, 5-tricarboxylic acid (trimesitic acid).

In addition to the structural units derived from the monomer components a) to f), polyesters A can also contain further structural units g) which are derived from monomers which are copolymerizable with the monomers a) to f), the monomers g) being derived from the monomers a) to f ) differentiate. The molar proportion of these further structural units g) in polyester A is usually 0 to 10%, in particular 0 to 5%. Polyesters A particularly preferably contain no further structural units g). Examples of monomers g) are diamines, bisphenols, polyester-forming phosphorus compounds or polyester-forming sulfur compounds.

To prepare the polyesters A or B, individual monomer components or mixtures of different compounds corresponding to one monomer component can be used.

Polyester A contains at least one structural unit with an ionic group. These structural units are derived from the monomer units b) or e). At least one of these monomer units, if appropriate also both of these monomer units, are used for the production of polyester A.

Polyester B does not contain a structural unit with an ionic group. In the production of polyester B, only monomer units a), c) and d) are used, and optionally crosslinkers f) and optionally other monomers g′).

In addition to the structural units derived from the monomer components a), c), d) and f), polyesters B can also contain further nonionic structural units g′) which are derived from monomers which are copolymerizable with the monomers a), c), d) and f). , where the monomers g') differ from the monomers a), c), d) and f). The molar proportion of these further structural units g′) in polyester B is usually 0 to 10%, in particular 0 to 5%. Polyesters B particularly preferably contain no further structural units g′). Examples of monomers g') are diamines, bisphenols, polyester-forming phosphorus compounds or polyester-forming sulfur compounds.

The molar proportion of component a), based on the total polyester A, is generally from 20 to 50%, particularly preferably from 25 to 45% and very particularly preferably from 35 to 42%.

The molar proportion of component b), based on the total polyester A, is generally from 0 to 40%, particularly preferably from 5 to 25% and very particularly preferably from 10 to 20%.

The molar proportion of component c), based on the total polyester A, is generally from 20 to 60%, particularly preferably from 25 to 55% and very particularly preferably from 35 to 48%.

The molar proportion of component d), based on the total polyester A, is generally from 0.5 to 40%, particularly preferably from 1 to 20% and very particularly preferably from 4 to 10%.

The molar proportion of component e), based on the total polyester A, is generally from 0 to 10%, particularly preferably from 1 to 8% and very particularly preferably from 2 to 5%.

The molar proportion of component f), based on the total polyester A, is generally from 0 to 10%, particularly preferably from 0 to 5% and very particularly preferably from 0 to 3%.

Particularly preferred polyesters A are uncrosslinked.

The molar proportion of component a), based on the total polyester B, is generally from 20 to 60%, particularly preferably from 30 to 55% and very particularly preferably from 35 to 50%.

The molar proportion of component c), based on the total polyester B, is generally from 10 to 50%, particularly preferably from 15 to 45% and very particularly preferably from 20 to 40%.

The molar proportion of component d), based on the total polyester B, is generally from 1 to 50%, particularly preferably from 10 to 40% and very particularly preferably from 15 to 35%.

The molar proportion of component f), based on the total polyester B, is generally from 0 to 10%, particularly preferably from 0 to 5% and very particularly preferably from 0 to 3%.

Particularly preferred polyesters B) are uncrosslinked.

Preferred compositions contain polyesters A and/or B in which component a) is selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, their alkali metal salts or alkaline earth metal salts or their dialkyl esters.

Further preferred compositions contain polyesters A, in which component b) is selected from the group consisting of sulfoterephthalic acid, sulfoisophthalic acid, sulfonaphthalenedicarboxylic acid, their alkali metal salts or alkaline earth metal salts or their dialkyl esters.

Further preferred compositions contain polyesters A and/or B, in which component c) is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol or a mixture ments of two or more thereof, preferably ethylene glycol, 1,2-propylene glycol or mixtures thereof and most preferably ethylene glycol.

Further preferred compositions contain polyesters A and/or B in which component d) is a compound of formula (2a). R ³ O(CHR ⁴ CHR ⁵ O) _t H (2a) whereby
R ³ is a linear or branched alkyl group with 1 to 6 carbon atoms, in particular with 1 to 3 carbon atoms,
R ⁴ and R ⁵ independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and
t is a number from 1 to 50, preferably from 12 to 30.

Further preferred compositions contain polyester A in which component e) is a compound of formula (3a). ^MeO3S- ( _CHR6CHR7O ) ^uH ( _3a ) whereby
Me is hydrogen, a monovalent metal cation or an ammonium cation,
R ⁶ and R ⁷ independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and
u is a number from 1 to 50, preferably from 1 to 5 and most preferably from 1 or 2.

Further preferred compositions contain polyester A in which component e) is a compound of formula (3b). _{MeO3 SC6} ^H4 _-COOR11 (3b) whereby
Me is hydrogen, a monovalent metal cation or an ammonium cation, preferably hydrogen or a sodium cation, and
R ¹¹ is hydrogen, a monovalent metal cation or an ammonium cation, preferably hydrogen or a sodium cation, and wherein
the sulfonyl group is located in particular in the 4-position of the phenyl ring.

Further preferred compositions contain polyester A in which component e) is a mixture of the compounds of formulas (3a) and (3b) defined above.

worin
y eine Zahl von 3 bis 6 ist,
R⁸ ein drei- bis sechswertiger organischer Rest, vorzugsweise ein drei- bis sechswertiger Alkyl- oder Arylrest ist, und
X -O- und/oder -COO- bedeutet und worin
der molare Anteil an von Komponente f) abgeleiteten Struktureinheiten im Polyester, bezogen auf die Gesamtmenge an Struktureinheiten im Polyester, 0 bis 5 Mol %, vorzugsweise 0 bis 3 Mol % und ganz besonders bevorzugt 0 bis 1 Mol % beträgt.Still other preferred compositions contain polyesters A and/or B in which structural units derived from component f) have the formula (6) or are derived from polyacrylic acid, polymaleic acid or from maleic acid-ethylene copolymers

wherein
y is a number from 3 to 6,
R ⁸ is a tri- to hexavalent organic radical, preferably a tri- to hexavalent alkyl or aryl radical, and
X is -O- and/or -COO- and wherein
the molar proportion of structural units derived from component f) in the polyester, based on the total amount of structural units in the polyester, is 0 to 5 mol%, preferably 0 to 3 mol% and very particularly preferably 0 to 1 mol%.

worin R C₁-C₄-Alkyl ist,
M Wasserstoff oder ein ein- oder zweiwertiges Kation bedeutet, i 1 oder 2 ist,
x 0,5 oder 1 bedeutet und das Produkt i . x = 1 ist, und
z eine Zahl von 3 bis 35 bedeutet, und die Zusammensetzungen enthalten Polyester B mit wiederkehrenden Struktureinheiten der oben definierten Formel Ia und mit Endgruppen der Formel V oder Polyester B mit wiederkehrende Struktureinheiten der oben definierten Formeln Ia und Ib und mit Endgruppen der Formel V

worin R⁹ Wasserstoff oder C₁-C₄-Alkyl ist, und
c eine Zahl von 1 bis 50, vorzugsweise 1 bis 35 bedeutet.In a particularly preferred embodiment, the compositions according to the invention contain polyesters A with recurring structural units of the formula Ia and with end groups of the formula II and the formula III or with end groups of the formula II and the formula IV or with end groups of the formula II, III and IV or the compositions contain polyester A with recurring structural units of the formula Ia and the formula Ib and with end groups of the formula II and the formula III or with end groups of the formula II and the formula IV or with end groups of the formula II, III and IV

wherein RC is ₁ -C ₄ alkyl,
M is hydrogen or a mono- or divalent cation, i is 1 or 2,
x is 0.5 or 1 and the product i . x = 1, and
z is a number from 3 to 35, and the compositions contain polyester B having repeating structural units of the formula Ia defined above and having end groups of the formula V or polyester B having repeating structural units of the formulas Ia and Ib defined above and having end groups of the formula V

wherein R ⁹ is hydrogen or C ₁ -C ₄ alkyl, and
c is a number from 1 to 50, preferably from 1 to 35.

worin M Wasserstoff oder ein ein- oder zweiwertiges Kation bedeutet, i 1 oder 2 ist,
x 0,5 oder 1 bedeutet und das Produkt i · x = 1 ist.In a further particularly preferred embodiment, the compositions according to the invention contain polyesters A which, in addition to the above-defined recurring structural units of the formula Ia or of the formulas Ia and Ib and the above-defined end groups of the formulas II and III or of the formulas II and IV or of the formulas II, III and IV contain the structural units of the formula Va and/or the formula Via or the structural units of the formulas Va and Vb and/or the formulas Via and Vlb

where M is hydrogen or a mono- or divalent cation, i is 1 or 2,
x means 0.5 or 1 and the product i x = 1.

The proportion of recurring structural units of the formula Ia or of recurring structural units of the formulas Ia and Ib or of recurring structural units of the formulas Ia, Va and/or Vb and/or Via and/or Vlb or of recurring structural units of the formulas Ia, Ib, Va and / or Vb and / or Via and / or Vlb in the polyesters A is usually 80 to 100 mol%, preferably 90 to 100 mol%, based on the total amount of recurring structural units in polyester A.

The proportion of recurring structural units of the formula Ia or of recurring structural units of the formulas Ia and Ib in the polyesters B is usually 80 to 100 mol%, preferably 90 to 100 mol%, based on the total amount of the recurring structural units in polyester B.

The proportion of recurring structural units of the formulas Va and / or Via or the formulas Va and Vb and / or the formulas Via and Vlb in the polyesters A is usually 0 to 15 mol%, preferably 1 to 15 mol%, particularly preferably 3 to 10 Mol%, and most preferably 5 to 8 mol%, based on the total amount of repeating structural units in polyester A.

The proportion of recurring structural units of the formulas Va and / or Via or the formulas Va and Vb and / or the formulas Via and Vlb in the polyesters B is usually 0 to 15 mol%, preferably 1 to 15 mol%, particularly preferably 3 to 10 Mol%, and most preferably 5 to 8 mol%, based on the total amount of repeating structural units in polyester B.

The proportion of end groups of the formulas II and III or of the formulas II and IV or of the formulas II, III and IV in the polyesters A is usually 80 to 100 mol%, preferably 90 to 100 mol%, based on the total amount of the end groups in polyester A .

The proportion of end groups of V in the polyesters B is usually 80 to 100 mol%, preferably 90 to 100 mol%, based on the total amount of end groups in polyester B.

In a further particularly preferred embodiment, the compositions according to the invention contain polyesters B of the following formula X'-[(OCH ₂ CH ₂ )q1-]-block-[(OCH ₂ CH(CH ₃ )) _p1 ]-[(OC (O) ^-R1a -C(O) ^OR2a ) _n1 ]-OC(O) ^-R1a -C(O)O-[((CH3 _{) CHCH2} O) _p1 -]-block-[(CH ₂ CH ₂ O) _q1 ]-X'
wherein
the R ^1a radicals are 1,4-phenylene groups,
the R ^2a radicals are ethylene or 1,2-propylene groups,
the radicals X' are C _1-4 -alkyl groups, preferably methyl or n-butyl,
q1 is a number from 12 to 120,
p1 is a number from 11 to 60, preferably from 15 to 50, and more preferably from 20 to 40, and
n1 is a number from 2 to 10.

The block copolyesters B of the above formula are linear block copolyesters.

Particular preference is given to those block copolyesters B of the above formula in which n1 is a number from 3 to 9, in particular from 3 to 5, very particularly preferably those derived from dimethyl terephthalate and 1,2-propylene glycol.

Block copolyesters B of the above formula in which p1 is a number from 11 to 50 and q1 is a number from 18 to 60 are also particularly preferred.

Block copolyesters B of the formula below are very particularly preferred C ₄ H ₉ -[(OCH ₂ CH ₂ ) ₅₀ -]-block-[(OCH ₂ CH(CH ₃ )) ₃₀ ]-[(OC(O)-C ₆ H ₄ -C(O)O-[ CH(CH ₃ )CH ₂ - OC(O)-C ₆ H ₄ -C(O)O] _n2 - wherein
n2 is a number from 2 to 15, preferably from 2 to 12, particularly preferably from 3 to 9 and very particularly preferably from 4 to 9, and the
C ₆ H ₄ radicals are derived from terephthalic acid or esters thereof.

Such polyesters are, for example, from EP 2670786 B1 famous.

In a very particularly preferred embodiment, the compositions according to the invention contain polyesters A which are derived from dimethyl terephthalate, dimethyl 5-sulfoisophthalate sodium salt, ethylene glycol and/or 1,2-propylene glycol and whose end groups are derived from sodium isethionic acid salt and from polyethylene glycol monomethyl ether, preferably from polyethylene glycol monomethyl ether with a molecular weight of 500 to 6000 g/mol, and in particular of polyethylene glycol monomethyl ether with a molecular weight of 700 to 2000 g/mol, and polyester B, which are derived from dimethyl terephthalate ethylene glycol and/or 1,2-propylene glycol and whose end groups are derived from Polyethylene glycol monomethyl ether, in particular polyethylene glycol monomethyl ether with a molecular weight of 700 to 2000 g/mol.

The polyesters A and B used according to the invention generally have number-average molecular weights in the range from 700 to 50,000 g/mol, preferably from 800 to 30,000 g/mol, in particular 1,000 to 25,000 g/mol, particularly preferably 1,200 to 15,000 g/mol.

The number average molecular weight is determined by size exclusion chromatography in aqueous solution using a calibration with narrow-distribution polystyrene sulfonic acid sodium salt standards. Such standards are commercially available, for example from PSS, Mainz. The molecular weight data in this description relate to the number-average molecular weight.

The polyesters A and B used according to the invention can be synthesized by processes known per se by polycondensation of components a) to g).

Expediently, the above components are first heated with the addition of a catalyst at normal pressure to temperatures of 160 to about 250° C. using an inert atmosphere, preferably in the presence of a salt of a C ₁ -C ₄ -alkyl carboxylic acid, in particular a dehydrated one or partially hydrated sodium acetate CH ₃ COONa x (H ₂ O) _x , where x is a number ranging from 0 to 6, and wherein this salt is present in amounts by weight of from 0.0001% to 10%, preferably from 0.01% to 5%, particularly preferably from 0.03% to 0.1%, based on the total amount of the monomers used and the ester of the carboxylic acid is used. The required molecular weights are then obtained in vacuo at from 160 to 250° C. by distilling off superstoichiometric amounts of the glycols used. The known transesterification and condensation catalysts of the prior art are suitable for the reaction, such as, for example, titanium tetraisopropylate, dibutyltin oxide, alkali or alkaline earth metal alkoxides or antimony trioxide/calcium acetate or mixtures of different catalysts. The amount of catalysts can be from 0.0001% to 10%, preferably from 0.01% to 5%, particularly preferably from 0.03% to 0.5%, based on the total amount of the monomers used and the ester of the carboxylic acid, be.

A preferred process for preparing the polyesters A and B used according to the invention is characterized in that the condensation of the components is carried out in a one-pot process, with the transesterification and condensation catalysts being added before the heating.

The polyesters A and B used according to the invention are readily soluble in water, show no tendency to hydrolysis at neutral or slightly acidic pH and form stable compositions which show little or no degradation and thus loss of performance even under more severe external conditions (storage at 45° C.).

In addition, the polyesters used according to the invention show excellent dispersing power for grease and other soiling of fibers and thus counteract the graying of the textiles. The performance in terms of increasing primary detergency, soil release activity and hydrophilization of nonionic polyesters is not inferior to solid anionic types.

The polyester compositions according to the invention can be prepared by dissolving the appropriate amount of polyester in a combination of water with water-miscible (cyclo)aliphatic alcohols.

In an alternative variant for the preparation of the polyester compositions according to the invention, components C) and D) can already be present during the synthesis of the polyester A) and polyester B) is added to the reaction mixture after the synthesis has taken place.

(Cyclo)aliphatic alcohols containing 1 to 20 carbon atoms are used as component C). Alcohols with one or more hydroxy groups can be used. The alcohols can be primary, secondary, or tertiary alcohols.

Aliphatic alcohols having one to four hydroxyl groups and one to ten, particularly preferably one to six, carbon atoms are preferred. Also preferred are cycloaliphatic alcohols having one or two hydroxy groups and five to six carbon atoms.

Examples of aliphatic alcohols having one to four hydroxyl groups and one to six carbon atoms are methanol, ethanol, propanol, butanol, pentanol, hexanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol , butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, butane-2,3-diol, pentane-1,5-diol, hexane-1,6-diol, ethylene glycol monomethyl ether , diethylene glycol, diethylene glycol monomethyl ether, triethylene glycol, trimethylolpropane, glycerin and penthaerythritol.

Examples of cycloaliphatic alcohols having one hydroxy group and five to six carbon atoms are cyclopentanol and cyclohexanol.

Preferred components C) are methanol, ethanol, n-propanol, isopropanol, glycerol, ethylene glycol, propanediol, diethylene glycol and triethylene glycol.

The polyesters can be introduced directly or in portions into the water/alcohol mixture initially taken for the solution at temperatures of 10 to 90° C., preferably 30 to 70° C., particularly preferably 50 to 60° C., and completely dissolved by stirring.

To improve the solubility of the polyesters, low molecular weight dispersants (hydrotropes) can also be added before or during the dissolving process.

Alkylbenzenesulfonates are preferably used here, such as sodium cumenesulfonate, sodium xylenesulfonate or sodium toluenesulfonate. It proved useful to combine these hydrotropes in one Amount of 0.1 to 30 wt .-%, preferably 1 to 15 wt .-%, based on the total weight of the composition to use.

The polyester compositions according to the invention are stable for several months when stored at 5 to 45.degree. The viscosities of the compositions according to the invention are in the range from 15 to 15,000 mPas, preferably in the range from 100 to 8000 mPas, particularly preferably in the range from 300 to 1000 mPas.

The viscosities are measured using a Brookfield viscometer at 100 spindle revolutions per minute at 20.degree. The spindle used is adjusted depending on the viscosity range. The compositions according to the invention are milky white to slightly yellowish to opaque.

The polyester compositions according to the invention give textile fibers very good dirt-removing properties, they significantly support the dirt-removing ability of the other detergent ingredients against oily, greasy or pigmented soiling and prevent particles from the washing liquor (especially lime soap and dirt pigments) from being deposited on the textile (greying).

A further subject of the invention is the use of the polyester compositions according to the invention in detergents and cleaning agents, in after-treatment agents for laundry, in particular in a fabric softener, textile care agents and agents for finishing textiles.

Detergent and cleaning agent formulations containing the polyester compositions according to the invention can be in the form of paste, gel or liquid. Liquid detergents are particularly preferred.

Examples of this are heavy-duty detergents, delicate detergents, color detergents, wool detergents, curtain detergents or modular detergents.

Surprisingly, the polyester compositions according to the invention are also distinguished by outstanding drainage behavior, in particular when rinsing plastic, ceramic and glass and metal surfaces. When cleaning hard surfaces, it reduces the tendency to form limescale deposits and reduces re-soiling of the treated surface, makes it difficult for oil and dirt to adhere and makes it easier to clean the surfaces again. The use of the polyester compositions according to the invention in the drying of crockery and cutlery proved to be particularly advantageous.

The polyester compositions according to the invention can thus also be used in household cleaning agents, for example all-purpose cleaners, dishwashing detergents, rinse aids, carpet cleaning and impregnating agents, cleaning and care products for floors and other hard surfaces, e.g. made of plastic, ceramic, glass, stone, metal or surfaces coated with nanoparticles be incorporated.

Examples of technical cleaning agents are plastic cleaning and care products, such as for housing and car fittings, as well as cleaning and care products for painted surfaces such as car bodies.

Depending on their intended use, the composition of the formulations should be adapted to the type of textiles to be treated or washed or to the surfaces to be cleaned.

The detergent and cleaning agent formulations can contain common ingredients such as surfactants, emulsifiers, builders, bleach catalysts and activators, sequestering agents, graying inhibitors, dye transfer inhibitors, dye fixatives, enzymes, optical brighteners, and softening components. In addition, formulations or parts of the formulation can be specifically colored and/or perfumed by dyes and/or fragrances.

examples

The following examples illustrate the invention without limiting it.

Polyester A (anionic component)

The preparation and composition of the anionic polyester component A can be found in example 1 of the patent EP 3 222 647 B1 be removed. This is, for example, a polyester which was produced by polycondensation of dimethyl terephthalate, dimethyl 5-sulfoisophthalate sodium salt, ethylene glycol and 1,2-propylene glycol and which had end groups derived from sodium salt of isethionic acid and from polyethylene glycol monomethyl ether

Polyester B (nonionic component)

The composition of the nonionic polyester components B is given in the table below. They are produced analogously to the anionic polyester component, with the difference that no monomers with ionic groups are used for the synthesis. The process of melt condensation is known to the expert.

The following polyesters B were used for the examples, the data being in moles: terephthalic acid 1,2-propanediol 1,2-ethanediol MPEG ^*) 750 MPEG ^*) 2000 no 1 3 2 - - 2 - - no 2 5 4 - - -- 2 no 3 6 4 1 2 - - nio 4 3 2 - - 1 1
^*) MPEG = polyethylene glycol monomethyl ether with an average molecular weight of 750 or 2000

Comparative example:

280 g of 1,2-propanediol and 80 g of 1,2,3-propanetriol are placed in a heatable 1 liter Büchi autoclave equipped with an impeller stirrer, internal thermometer and reflux condenser. 15 g of distilled water are added to the mixture of polyols, rendered inert with nitrogen and then heated to 55° C. with stirring. Thereafter, 58 g of the anionic polyester component polyester A (for definition see above) are added in small portions as a powder (particle size <1000 μm) to the solution in a nitrogen countercurrent over the course of 30 minutes. Initially, a slight opalescence develops within the solution, which changes to a milky white composition within 30 minutes. After the addition is complete, the mixture is stirred at 55° C. for a further 60 minutes and then the composition is discharged into a suitable vessel via the bottom valve of the stirred autoclave.

The viscosity of the composition at 20° C. measured using a Brookfield viscometer (spindle 3, 100 rpm) is 15,000 mPa*s. The suspension solidified after just 1 hour (viscosity >45,000 mPas). A further measurement of the viscosity after 3 months was no longer possible with the Brookfield method (> 100,000 mPas)

Example 1:

300 g of diethylene glycol and 85 g of 1,2,3-propanetriol are placed in a heatable 1 liter Büchi autoclave equipped with an impeller stirrer, internal thermometer and reflux condenser. 24 g of distilled water are added to the mixture of polyols, rendered inert with nitrogen and then heated to 50° C. with stirring. After the target temperature has been reached, 53.6 g of a 70% strength solution of the nonionic polyester B (Nio 1) are added with stirring. A clear solution of the components forms. The solution is heated to 55°C.

Thereafter, 37.5 g of the anionic polyester component polyester A (see above for definition) are added in small portions as a powder (particle size <1000 μm) to the solution in a nitrogen countercurrent over the course of 30 minutes. Initially, a slight opalescence develops within the solution, which changes to a milky white composition within 30 minutes. After the addition is complete, the mixture is stirred at 55° C. for a further 60 minutes and then the composition is discharged into a suitable vessel via the bottom valve of the stirred autoclave.

The viscosity of the composition at 20° C. measured using a Brookfield viscometer (spindle 3, 100 rpm) is 350 mPa*s. After storage for three months, the viscosity of the suspension was determined to be 600 mPa*s (measured on a sample heated to 20° C.).

Example 2:

192.5 g of 1,2-propanediol and 192.5 g of 1,2-ethanediol are placed in a heatable 1 liter Büchi autoclave equipped with an Intermig stirrer, internal thermometer and reflux condenser. 24 g of distilled water are added to the mixture of polyols, rendered inert with nitrogen and then heated to 50° C. with stirring. After the target temperature has been reached, 50 g of a 75% solution of the nonionic polyester B (Nio2) are added with stirring. A clear solution of the components forms. The solution is heated to 52°C.

37.5 g of the anionic polyester component polyester A (for definition see above) is added in small portions as a powder (particle size <1200 μm) to the solution in a nitrogen countercurrent over the course of 30 minutes. A slight opalescence initially develops within the solution, which changes to a milky white composition within 30 minutes. After the addition is complete, the mixture is stirred at 55° C. for a further 60 minutes and then the composition is discharged into a suitable vessel via the bottom valve of the stirred autoclave.

The viscosity of the composition at 20° C. measured using a Brookfield viscometer (spindle 2, 100 rpm) is 170 mPa*s. After 2 months of warm storage at 45°C, a viscosity of 400 mPa*s was determined (measured at 20°C).

Example 3:

250 g of 1,2-propanediol and 115 g of 1,2,3-propanetriol are placed in a heatable 1 liter Büchi autoclave equipped with an Intermig stirrer, internal thermometer and reflux condenser. 22 g of distilled water are added to the mixture of polyols, rendered inert with nitrogen and then heated to 50° C. with stirring. After the target temperature has been reached, 40 g of a 70% strength solution of the nonionic polyester B (Nio1) are added with stirring. A clear solution of the components forms.

In addition, 56.7 g of a second nonionic polyester 2 (Nio3) are added as a 75% solution in water to the glycol/water mixture. The solution is heated to 52°C.

44.5 g of the anionic polyester component polyester A (for definition see above) are added in small portions as a powder (particle size <1200 μm) to the solution in a nitrogen countercurrent over the course of 30 minutes. Initially, a slight opalescence develops within the solution, which changes to a milky white composition within 30 minutes. After the addition is complete, the mixture is stirred at 55° C. for a further 60 minutes and then the composition is discharged into a suitable vessel via the bottom valve of the stirred autoclave.

The viscosity of the composition at 20° C. measured using a Brookfield viscometer (spindle 3, 100 rpm) is 820 mPa*s. After storage for three months at 45° C., the viscosity rose to 900 mPa*s. The measurement was carried out after the sample had been heated to 20°C.

Example 4:

200 g of 1,2-propanediol, 100 g of 1,2-ethanediol and 70 g of 1,2,3-propanetriol are placed in a heatable 1 liter Büchi autoclave equipped with an impeller stirrer, internal thermometer and reflux condenser. 16 g of distilled water are added to the mixture of polyols, rendered inert with nitrogen and then heated to 50° C. with stirring. After the target temperature has been reached, 25 g of a 70% strength solution of the nonionic polyester B (Nio1) are added with stirring. A clear solution of the components forms. In addition, a second nonionic polyester B (Nio4) is added to the solution. The solution is heated to 50°C.

45 g of the anionic polyester component polyester A (for definition see above) is added in small portions as a powder (particle size <1200 μm) to the solution in a nitrogen countercurrent over the course of 30 minutes. Initially, a slight opalescence develops within the solution, which disappears within 30 minutes into a milky white composition. After the addition is complete, the mixture is stirred at 55° C. for a further 60 minutes and then the composition is discharged into a suitable vessel via the bottom valve of the stirred autoclave.

The viscosity of the composition at 20° C., measured using a Brookfield viscometer (spindle 3, 100 rpm), is 650 mPa*s directly after preparation. After two months of storage at 45°C in a closed vessel, the viscosity rose to 1500 mPa*s. The measurement was carried out after the sample had been heated to 20°C.

Example 5:

200 g of 1,2-propanediol and 100 g of 1,2-ethanediol are placed in a heatable 1 liter Büchi autoclave equipped with an impeller stirrer, internal thermometer and reflux condenser. 25 g of distilled water are added to the mixture of polyols, rendered inert with nitrogen and then heated to 50° C. with stirring. After the target temperature has been reached, 100 g of a 70% strength solution of the nonionic polyester B (Nio1) are added with stirring. A clear solution of the components forms. In addition, a second nonionic polyester B (Nio4) is added to the solution. The solution is heated to 50°C.

20 g of the anionic polyester component polyester A (for definition see above) is added in small portions as a powder (particle size <1200 μm) to the solution in a nitrogen countercurrent within 30 minutes. A slight opalescence initially develops within the solution, which changes to a milky white composition within 30 minutes. After the addition is complete, the mixture is stirred at 55° C. for a further 60 minutes and then the composition is discharged into a suitable vessel via the bottom valve of the stirred autoclave.

The viscosity of the composition at 20° C., measured using a Brookfield viscometer (spindle 3, 100 rpm), is 900 mPa*s directly after preparation. After two months of storage at 45°C in a closed vessel, the viscosity rose to 1800 mPa*s. The measurement was carried out after the sample had been heated to 20°C.

Example 6:

400 g of diethylene glycol and 100 g of 1,2-ethanediol are placed in a heatable 1 liter Büchi autoclave equipped with an impeller stirrer, internal thermometer and reflux condenser. 15 g of distilled water are added to the mixture of polyols, rendered inert with nitrogen and then heated to 50° C. with stirring. After the target temperature has been reached, 50 g of a 70% strength solution of the nonionic polyester B (Nio1) are added with stirring. A clear solution of the components forms. In addition, a second nonionic polyester B (Nio4) is added to the solution. The solution is heated to 50°C.

18 g of the anionic polyester component polyester A (for definition see above) is added in small portions as a powder (particle size <1200 μm) to the solution in a nitrogen countercurrent over the course of 30 minutes. Initially, a slight opalescence develops within the solution, which changes to a milky white composition within 30 minutes. After the addition is complete, the mixture is stirred at 55° C. for a further 60 minutes and then the composition is discharged into a suitable vessel via the bottom valve of the stirred autoclave.

The viscosity of the composition at 20° C., measured using a Brookfield viscometer (spindle 3, 100 rpm), is 900 mPa*s directly after preparation. After two months of storage at 45°C in a closed vessel, the viscosity rose to 1800 mPa*s. The measurement was carried out after the sample had been heated to 20°C.

QUOTES INCLUDED IN DESCRIPTION

This list of documents cited by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent Literature Cited

• US4702857A [0004]
• US4427557A [0004]
• US4721580A [0004]
• US4968451A [0004]
• WO 9618715 A2 [0004]
• US5415807A [0004]
• US5691298 [0004]
• DE 19906367 A1 [0004]
• WO 9805747 A1 [0004]
• US5599782A [0004]
• WO 9422937 A1 [0004]
• EP 1966273 B1 [0004]
• EP 2504380 A1 [0004]
• WO 2011/063945 A1 [0009, 0010]
• EP 3167032 B1 [0010]
• EP 2670786 B1 [0029, 0034, 0081]
• EP 3222647 B1 [0112]

Claims (20)

Compositions containing A) at least one anionic polyester obtainable by polymerization of the components a) one or more sulfo-free aromatic dicarboxylic acids and/or their salts and/or their anhydrides and/or their esters, b) optionally one or more sulfo-containing dicarboxylic acids, their salts and/or or their anhydrides and/or their esters, c) one or more aliphatic diols of the formula (1) H-(OC _m H _2m ) _s -OH (1), where m is a number from 2 to 10 and m can have different meanings within a molecule within the scope of the given definition, s is a number from 1 to 200, where s is at least 1 and can also have a value between 2 and 200, d ) optionally one or more compounds of formula (2) R ¹ O(C _o H _2o O) _p H (2) where R ¹ is a linear or branched alkyl group having 1 to 22 carbon atoms, o is a number from 2 to 10 and o can have different meanings within a molecule within the scope of the given definition, p is a number from 1 to 200, e) optionally one or more compounds of the formula (3) and/or the formula (4) R ² (CqH _2q O) _r H (3), (Me ^a+ ) _{b -O3} ^SC6 H4 _-COOR10 ( ₄ ), where q is a number from 2 to 10, r is a number from 1 to 10 and R ² is a radical (Me ^a+ ) _b ^- OOC- or (Me ^a+ ) _b ^- O ₃ S-, R ¹⁰ is hydrogen or C ₁ -C ₆ -alkyl, Me is hydrogen or an a-valent cation, a is a number from 1 to 3, b is a number with the value 1/a, and f) optionally one or more crosslinking polyfunctional compounds, with the proviso that at least one of components b) or e) is present, B) at least one nonionic polyester obtainable by polymerization of components a), c), d) and optionally f), C) one or more aliphatic or cycloaliphatic alcohols with 1-20 carbon atoms, and D) water. compositions according to claim 1 , characterized in that the proportion by weight of the polyesters A) and B) in the composition is 1 to 50%, preferably 5 to 40%, in particular 10 to 30% and very particularly preferably 15 to 25%. Compositions according to at least one of Claims 1 or 2 , characterized in that the proportion by weight of the polyester A) in the total mass of the polyesters A) and B) is 20 to 80%, preferably 35 to 60% or that the proportion by weight of the polyester B) in the total mass of the polyesters A) and B) 80 to 20%, preferably 65 to 40%. Compositions according to at least one of Claims 1 until 3 , characterized in that component a) is selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, their alkali metal salts or alkaline earth metal salts or their dialkyl esters. Compositions according to at least one of Claims 1 until 4 , characterized in that component b) is selected from the group consisting of sulfoterephthalic acid, sulfoisophthalic acid, sulfonaphthalenedicarboxylic acid, their alkali metal salts or alkaline earth metal salts or their dialkyl esters. Compositions according to at least one of Claims 1 until 5 , characterized in that component c) is selected from the group consisting of ethylene glycol, propylene glycol or mixtures thereof, preferably ethylene glycol, 1,2-propylene glycol or mixtures thereof. Compositions according to at least one of Claims 1 until 6 , characterized in that component d) is a compound of formula (2a). _R ³ O(CHR ⁴ CHR ⁵ O) SH (2a) where R ³ is a linear or branched alkyl group having 1 to 6 carbon atoms, in particular having 1 to 3 carbon atoms, R ⁴ and R ⁵ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and s is a number from 1 to 50, preferably from 12 to 30. Compositions according to at least one of Claims 1 until 7 , characterized in that component e) is a compound of formula (3a). MeO ₃ S-(CHR ⁶ CHR ⁷ O) _t H (3a) where Me is hydrogen, a monovalent metal cation or an ammonium cation, R ⁶ and R ⁷ are independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and t is a number from 1 to 50, preferably from 1 to 5 and whole most preferably 1 or 2. Compositions according to at least one of Claims 1 until 7 , characterized in that component e) is a compound of formula (3b). _{MeO3 SC6} ^H4 _-COOR11 (3b) where Me is hydrogen, a monovalent metal cation or an ammonium cation, preferably hydrogen or a sodium cation, and R ¹¹ is hydrogen, a monovalent metal cation or an ammonium cation, preferably hydrogen or a sodium cation, and where the sulfonyl group is in particular in the 4-position of the phenyl ring is arranged. compositions according to claims 8 and 9 , characterized in that component e) is a mixture of the compounds of the formulas (3a) and (3b). Compositions according to at least one of Claims 1 until 10 , characterized in that the polyesters A and B are uncrosslinked. Compositions according to at least one of Claims 1 until 11 , characterized in that polyester A) contains recurring structural units of the formula Ia and end groups of the formula II and the formula III or end groups of the formula II and the formula IV or end groups of the formula II, III and IV or recurring structural units of the formula Ia and the formula Ib and end groups of the formula II and the formula III or end groups of the formula II and the formula IV or end groups of the formula II, III and IV

wherein RC is ₁ -C ₄ alkyl, M is hydrogen or a mono- or divalent cation, i is 1 or 2, x is 0.5 or 1 and the product i x is 1, and z is a number of 3 to 35, and that polyester B) contains recurring structural units of the formula Ia defined above and end groups of the formula V or contains recurring structural units of the formula Ia defined above and of the formula Ib and end groups of the formula V,

wherein R ⁹ is hydrogen or C ₁ -C ₄ alkyl, and c is a number from 1 to 35. compositions according to claim 12 , characterized in that polyester A) in addition to the recurring structural units of the formula Ia or of the formulas Ia and Ib and the end groups of the formulas II and III or of the formulas II and IV or of the formulas II, III and IV, the structural units of the formula Va and / or of the formula Via or the structural units of the formulas Va and Vb and/or of the formulas Via and Vlb

wherein M is hydrogen or a mono- or divalent cation, i is 1 or 2, x is 0.5 or 1 and the product i x x =1. compositions according to claim 12 or 13 , characterized in that the proportion of recurring structural units of the formula Ia or of recurring structural units of the formulas Ia and Ib or of recurring structural units of the formulas Ia, Va and/or Vb and/or Via and/or Vlb or of recurring structural units of Formulas Ia, Ib, Va and/or Vb and/or Via and/or Vlb in polyester A) is 80 to 100 mol%, based on the total amount of recurring structural units in polyester A), and that the proportion of recurring structural units of the formula is Ia or of recurring structural units of the formulas Ia and Ib in polyester B) is 80 to 100 mol%, based on the total amount of recurring structural units in polyester B). compositions according to claim 12 , 13 or 14 , characterized in that the proportion of end groups of the formulas II and III or of the formulas II and IV or of the formulas II, III and IV in polyester A) is 80 to 100 mol%, based on the total amount of end groups in polyester A), and that the proportion of end groups of V in polyester B) is 80 to 100 mol %, based on the total amount of end groups in polyester B). Compositions according to at least one of Claims 1 until 15 , characterized in that polyester A) is derived from dimethyl terephthalate, dimethyl 5-sulfoisophthalate sodium salt, ethylene glycol and/or 1,2-propylene glycol and that their end groups are derived from sodium isethionic acid salt and from polyethylene glycol monomethyl ether, and that polyester B is derived from dimethyl terephthalate , ethylene glycol and/or 1,2-propylene glycol and that their end groups are derived from polyethylene glycol monomethyl ether. Compositions according to at least one of Claims 1 until 16 , characterized in that component C) is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, glycerol, ethylene glycol, propanediol, diethylene glycol, triethylene glycol and mixtures of two or more thereof. Detergents and cleaning agents containing a composition according to at least one of Claims 1 until 17 . Use of a composition according to any one of Claims 1 until 17 for washing textiles or for drying and cleaning hard surfaces. use after claim 19 , characterized in that the composition is used to improve the removal of dirt from textiles, to reduce resoiling, to protect the fibers under mechanical stress, to finish fabrics and to increase the wearing comfort.